104. THE PERILS OF 4.4 VOLTS

State-of-the-art lithium-ion batteries, whether used in smartphones or electric vehicles, all rely on the same fundamental cell structure: two opposing electrodes with an intermediate insulating separator layer, with lithium ions shuffling between the two electrodes.

The positive electrode during charging, usually called the cathode, consists of a multi-metal oxide alloy material. Lithium-cobalt-oxide, or LCO, is by far the most common for consumer electronic applications. NCM, short for lithium nickel-cobalt-manganese oxide, also known as NMC, is gradually replacing other materials in energy storage and electric vehicle applications. LCO and NCM have a great property of storing lithium ions within their material matrix. Think of a porous swiss cheese: the lithium ions insert themselves between the atomic layers.

In contrast, the anode, or negative electrode during charging, is almost universally made of carbon graphite. Carbon historically was and continues to be the material of choice. It has a large capacity to store lithium ions within its crystalline matrix, much like the metal oxide cathode.

So how do manufacturers increase energy density? In some respects, the math is simple. In practice, it gets tricky.

Energy density equals total energy stored divided by volume. The total stored energy is dictated by the amount of active material, i.e., the available amount of metal oxide alloy as well as graphite that can physically store the lithium ions (i.e., the electric charge). So battery manufacturers resort to all types of design tricks to reduce the volume of inactive material, for example, reducing the thickness of the separator and metal connectors. Of course, there are limits with safety topping the list. To a large extent, this is what battery manufacturers did for the past 20 years — amounting largely to about a 5% increase annually in energy density.

But once this extra volume of inactive material is reduced to its bare minimum, increasing energy density gets tricky and challenging. This is the difficult wall that the battery industry is facing now. So what is next?

There are two potential paths forward:

1. Find a way to pack more ions (i.e., more electric charge) within the electrodes. This is the topic of much research to develop new materials capable of such feat. But any such breakthrough is still several years away from commercial deployment, leaving the second option to….

2. Increase the voltage. Since energy equals charge multiplied by voltage, increasing the voltage also raises the amount of energy (remember that energy and charge are related but are not commutable). This is the object of today’s post.

The battery industry raised the voltage a few years back from a maximum of 4.2 V to the present-day value of 4.35 V. This was responsible for adding approximately 4 to 5% to the energy density. A new crop of batteries is now beginning to operate at 4.4 V, adding an additional 4 to 5% to the energy density. But that does not come without some serious challenges. What are they?

First, there is the electrolyte. It is a gel-like solvent that imbibes the inside of the battery. Short of a better analogy, if ions are like fish, then the electrolyte is like water. It is the medium within which the lithium ions can travel between the two electrodes. As the voltage rises, it subjects the electrolyte to increasingly higher electric fields causing its early degradation and breakdown. So we are now seeing a new generation of electrolytes that can in principle withstand the higher voltage — albeit, we see in our lab testing that some of these electrolyte formulations are responsible for worse cycle life performance. This is a first example of the compromises that battery designers are battling.

Second, there is the structural integrity of the cathode. Let’s take LCO as an example. If we peer a little closer into the cathode material (see the figure below), we find a crystal structure with layers made of cobalt and oxygen atoms. When the battery is fully discharged, the lithium ions occupy the vacant space between these ordered layers. In fact, there is a proportion of lithium ions to cobalt and oxygen atoms: there is one lithium ion for every one cobalt and two oxygen atoms.

courtesy of visualization for electronic and structural analysis (VESTA)

As the battery is charged, the lithium ions leave the cathode to the anode vacating some of the space between the ordered layers of the LCO cathode. But not all the lithium ions can leave; if too many of them leave, then the crystal structure of the cathode collapses and the material changes its properties. This is not good. So only about half of the lithium ions are “permitted” to leave during charging. This “permission” is determined by, you guessed it, the voltage. Right about 4.5 V, the LCO crystal structure begins to deteriorate, so one can easily see that at 4.4 V, the battery is already getting too close to the cliff.

Lastly, there is lithium plating. High energy-density cells push the limit of the design and tolerances in order to reduce the amount of material that is not participating in the storage. One of the unintended consequences is an “imbalance” between the amount of cathode and anode materials. This creates an “excess” of lithium ions that then deposit as lithium metal, hence plating.

These three challenges illustrate the increasing difficulties that battery manufacturing must overcome to continue pushing the limits of energy density. As they make progress, however, compromises become the norm. Cycle life is often shortened. Long gone are the days of 1,000+ cycles without intelligent adaptive controls. Fast charging becomes questionable. In some cases, safety may be in doubt. And the underlying R&D effort costs a lot of money with expenses that are stretching the financial limits of battery manufacturers without the promise of immediate financial returns in a market that is demanding performance at a the lowest possible price.

It is great to be a battery scientist with plenty of great problems to work on…but then again, may be not.